CN103894208A - Low noble metal mercury-free catalyst for acetylene hydrochlorination reaction, preparation method and application thereof - Google Patents
Low noble metal mercury-free catalyst for acetylene hydrochlorination reaction, preparation method and application thereof Download PDFInfo
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Abstract
This invention relates to a low noble metal mercury-free catalyst for a vinyl chloride synthesis reaction through an acetylene hydrochlorination reaction, a preparation method and an application thereof. The catalyst comprises an active carbon carrier and a mixed active component comprising one or a plurality of noble metal compounds and one or a plurality of general metal compounds according to a certain ratio, wherein the mass content of the noble metal is 0.01-0.04%, and the mass content of the general metal is 0.1-1%. The low noble metal mercury-free catalyst has characteristics of low noble metal content, low catalyst cost, high catalyst activity and long service life.
Description
Technical field
The present invention relates to low noble metal catalyst without mercury for acetylene hydrochlorination reaction and preparation method thereof, and use the method for low noble metal catalyst without mercury catalyzing acetylene preparing vinyl chloride by hydrochlorination of the present invention.
Background technology
Acetylene and hcl reaction can generate vinyl chloride, and vinyl chloride is the monomer of the synthetic use of igelite (PVC), and synthesizing of VCM is significant for PVC industry.Industrial processes are at present used activated carbon supported mercury chloride as catalyst, reaction temperature 100-200 ℃.Along with socioeconomic development, the output of igelite constantly increases, and the consumption of catalyst also constantly increases.Mercury is a kind of noxious material, and environmental pollution is serious.Therefore the course of reaction that goes out to send synthesizing chloroethylene from acetylene is received the dual-pressure of mercury resource and environmental protection.The catalyst without mercury of the environmental protection of development of new, the catalyst that current industrial process is used substitutes, and is the pressing problem that production of vinyl chloride by calcium carbide method industry faces.Current industrial is also all paid much attention to the development of catalyst without mercury with academia, have made some progress:
Chinese patent 200910196849.X discloses a kind of catalyst without mercury system, and the main active component of catalyst is golden salt, can be golden halide, complex compound etc., and in golden salt, gold content accounts for the 0.1-10% of catalyst weight; Helping active component is base metal salt, can be halide, acetate, phosphate, complex compound of potassium, barium, lanthanum, copper etc., and base metal salt content accounts for the 0.1-10% of catalyst weight; Carrier is active carbon, comprises coconut husk matter charcoal, ature of coal charcoal, shell matter charcoal, or silica gel.
Chinese patent 200910236255.7 discloses a kind of liquid phase catalyst without mercury system, and solvent is glyoxaline ion liquid, and catalyst is a kind of or its two or more any combination in the chloride of gold, platinum, palladium, tin, mercury, copper or rhodium.
Chinese patent 200910228149.4 discloses a kind of catalyst without mercury system, catalyst is take activated carbon as carrier, take the chloride that contains 2～15% palladium or gold as active component, 1～5% rare earth-iron-boron is cocatalyst component, is carried on the pellet type catalyst making on activated carbon through infusion process.
Chinese patent 201010149180.1 discloses a kind of catalyst without mercury system, and it is carrier that catalyst adopts active carbon, and dipping absorption barium salt is as active component.
Chinese patent 201010185916.0 discloses a kind of liquid phase catalyst without mercury system, and reaction dissolvent is pyridines ionic liquid, take tin, palladium, platinum, gold, copper, manganese, bismuth, mercury or rhodium muriatic one or more as active component.
Chinese patent 201010248348.4 discloses a kind of catalyst without mercury system, and catalyst is take active carbon and molecular sieve as carrier, and the chloride of noble ruthenium is active component, prepares by infusion process.
Chinese patent 201010272612.8 discloses a kind of low noble metal catalyst without mercury system, the base metals such as the noble metals such as catalyst employing gold, platinum, rhodium, ruthenium, palladium and copper, zinc, potassium, barium, nickel are active component, active carbon, molecular sieve, silica gel, CNT etc. are carrier, and the mass content of noble metal is at 0.05%-0.5%.Be applicable to the reactor such as fluid bed, fixed bed.
Chinese patent 201010574802.5 discloses a kind of catalyst without mercury system, catalyst is take cocoanut active charcoal as carrier, stannous chloride is main active substances, and the quality percentage composition of stannous chloride is 15%-30%, is added with at least one additive in barium chloride, zinc chloride and copper chloride.
Chinese patent 201110023364.8 discloses a kind of catalyst without mercury system, and catalyst is take Ni2P as activated centre, and take active carbon as carrier, auxiliary agent is iron chloride, nickel chloride, barium chloride.
Chinese patent 201110023357.8 discloses a kind of catalyst without mercury system, and it is carrier that catalyst adopts active carbon, and the bismuth simple substance of the bismuth trichloride being reduced is active component, the chloride auxiliary agent of ferrous iron, iron, nickel, barium, bismuth.
Chinese patent 201110040369.1 discloses a kind of catalyst without mercury system, and it is carrier that catalyst adopts active carbon, and active component is phosphorized copper, and auxiliary agent is one or more of copper chloride, nickel chloride, barium chloride.
Chinese patent 201110040371.9 discloses a kind of catalyst without mercury system, and it is carrier that catalyst adopts active carbon, and active component is phosphatization molybdenum, and auxiliary agent is barium chloride.
Chinese patent 201110040375.7 discloses a kind of catalyst without mercury system, and it is carrier that catalyst adopts active carbon, and active component is tungsten phosphide, and auxiliary agent is one or more of nickel chloride, barium chloride, copper chloride.
Chinese patent 201110150287.2 discloses a kind of catalyst without mercury system, it is carrier that catalyst adopts active carbon, and by ultrasonic processing, coupling agent equal solvent carries out carrier surface modification, load chlorauride or ruthenic chloride, take the chloride of bismuth, barium, manganese, iron etc. as auxiliary agent.
Chinese patent 201110199651.4 discloses a kind of catalyst without mercury system, it is carrier that catalysis adopts the porous microstructure materials such as active carbon, silica, the chloride of gold element, cobalt element, lanthanum element or nitrate are active component, and auxiliary agent is the chloride of potassium, sodium, bismuth, iron etc.
Chinese patent 201110257699.6 discloses a kind of catalyst without mercury system, catalyst take coconut husk charcoal, fruit shell carbon, do not have machine active carbon as carrier, active component is one or more of copper, nickel, bismuth, zinc-manganese, molybdenum.Metal is with form loads such as oxide, chloride, nitrate, acetate.
Chinese patent 201110257696.2 discloses a kind of catalyst without mercury system, and catalyst is take molecular sieve as carrier, the halide of supported precious metal palladium or complex compound.0.1-5％wt.
Chinese patent 201110257697.7 discloses a kind of catalyst without mercury system, and catalyst is take active carbon as carrier, and noble metal is active component, prepares by infusion process.
Chinese patent 201110291457.9 discloses a kind of catalyst without mercury system, and catalyst contains stannic chloride, rare earth-iron-boron, other metal chlorides, and rare earth-iron-boron is cerium chloride or lanthanum chloride, and carrier is cerium-zirconium powder, zirconia etc.
Chinese patent 201210100688.1 discloses a kind of catalyst without mercury system, one or more combination, the carrier active carbon that catalyst closes potassium aurate, auxiliary activity component potassium chloride, copper chloride, cobalt chloride and zinc chloride by main active component four thiocyanic acids forms, wherein gold complex accounts for 0.1～2.5% of catalyst weight, and auxiliary activity component accounts for 0.05～15% of total catalyst weight altogether.
In general, the catalyst without mercury system principal character of document and patent report is that catalyst employing active carbon or other oxide are carrier at present, the loaded catalyst of preparing by loading metal-salt, oxide or phosphide isoreactivity component.Wherein the highest, the good stability of the catalyst activity take Precious Metals-Gold, palladium, ruthenium, platinum etc. as active component.According to current bibliographical information, the load capacity of these noble metals could obtain higher activity and stability more than 0.05%, and therefore catalyst cost is higher, and commercial Application faces huge economy problems.The present invention is by metallic compounds such as a small amount of iron of load, zinc, copper, be equipped with the noble metals such as a small amount of gold, palladium, ruthenium, platinum and form composite reactive component, thereby the load capacity that realizes noble metal had both had good activity and stability in the time of 0.01-0.04%, the cost of catalyst is significantly reduced, there is the possibility of commercial Application.
Summary of the invention
For overcoming the problems of the prior art, the object of this invention is to provide one in acetylene hydrochlorination reaction, be especially low noble metal catalyst without mercury using in the reaction for the synthesis of vinyl chloride and preparation method thereof.
Therefore, aspect first, the invention provides a kind of low noble metal catalyst without mercury (below sometimes referred to as " catalyst of the present invention "), it comprises absorbent charcoal carrier; The mixed active component that one or more precious metal chemical complexs and one or more common metal compounds form according to a certain percentage, the 0.01-0.04% that wherein mass content of noble metal is described quality of activated carbon, the mass content of common metal is the 0.1-1% of described quality of activated carbon, described noble metal is selected from gold, palladium, ruthenium, platinum and iridium, described common metal chosen from Fe, zinc and copper.
In a preferred embodiment of catalyst of the present invention, the mass content of noble metal can be the 0.02-0.04% of described quality of activated carbon, and the mass content of common metal can be the 0.5-0.8% of described quality of activated carbon.
In the present invention, precious metal chemical complex can adopt its soluble-salt, preferably chloride, sulfate, phosphate, nitrate etc., more preferably chloride.
In the present invention, common metal compound can adopt its soluble-salt, preferably chloride, sulfate, phosphate, nitrate etc., more preferably chloride.
In a preferred embodiment, the vinyl chloride that catalyst of the present invention is realized in acetylene hydrochlorination reaction is selectively not less than 97%, preferably more than 98%.Simultaneously, catalytic activity and the catalytic selectivity of catalyst of the present invention in the time that acetylene hydrochlorination reaction is carried out 100 hours is constant (in the present invention, the implication of " constant " refers to that the variation between two numerical value of comparing is no more than 5% of previous numerical value, even 1%).
Aspect second, the invention provides a kind of preparation method of catalyst of the present invention, described method is carried out as follows: absorbent charcoal carrier is dry; Then take the soluble-salt of a certain amount of one or more noble metals and the soluble-salt of a certain amount of one or more common metals according to carried by active carbon weight, be dissolved in and in methyl alcohol or ethanol, obtain catalyst impregnating solution; Above-mentioned absorbent charcoal carrier is placed in to catalyst impregnating solution dipping, dries, obtain finished catalyst.
Aspect the 3rd, the invention provides a kind of method of utilizing low noble metal catalyst without mercury catalyzing acetylene preparing vinyl chloride by hydrochlorination of the present invention, the method is carried out as follows: a certain amount of described catalyst is placed in to tubular fixed-bed reactor, reaction temperature 120-220 ℃, pass into reaction raw materials gas hydrogen chloride and acetylene, reaction raw materials gas ratio is: the volume ratio=0.9-1.2 of hydrogen chloride/acetylene, the volume ratio=10-120h of reaction raw materials gas flow rate and catalyst
-1.
Beneficial effect of the present invention:
1. in catalyst of the present invention, the load capacity of noble metal is only 0.01-0.04 quality %, need to reach the required minimum content of enough activity lower than thinking in prior art, catalyst of the present invention has been realized the effect of the higher catalytic activity of under the condition of low noble metal load capacity acquisition.
2. catalyst stability of the present invention is good, and long-time (through after 100 hours) used its catalytic activity and selectively substantially constant.
3. catalyst cost of the present invention is low, and preparation technology is simple, is applicable to industrial large-scale application.
The specific embodiment
The invention provides a kind of low noble metal catalyst without mercury, it comprises absorbent charcoal carrier; The mixed active component that one or more precious metal chemical complexs and one or more common metal compounds form according to a certain percentage, the 0.01-0.04% that wherein mass content of noble metal is described quality of activated carbon, the mass content of common metal is the 0.1-1% of described quality of activated carbon, described noble metal is selected from gold, palladium, ruthenium, platinum and iridium, described common metal chosen from Fe, zinc and copper.
Noble metal salt, especially its chlorides such as gold, palladium, ruthenium, platinum and iridium have very high acetylene hydrochlorination reactivity and selective.Study and show at present, the activity of catalyst is directly proportional to the load capacity of noble metal, in the time of lower noble-metal-supported amount (< 0.1%), and the activity of catalyst lower (seeing comparative example 1).Therefore in current disclosed document, the load capacity of noble metal generally all exceedes 0.05%, just can obtain good catalytic activity.
The present invention proposes to use 0.1-1% common metal chloride as auxiliary agent, scheme cause using 0.01-0.04% precious metal chloride as main active component is: our research is found, when bullion content is higher than 0.05% time, the auxiliary agent effect of metal chloride is not obvious, when this is higher because of bullion content, the activity of precious metal chloride will be far above the chloride of common metal, the catalytic activity of precious metal chloride itself shows especially out, therefore (seeing contrast reaction embodiment 3,4) covered in the muriatic auxiliary catalysis effect of common metal; And in the time of the reduced levels of bullion content at 0.01-0.04%, can play electronics promoter effect by adding a small amount of common metal chloride, and obviously strengthen the activation process of catalyst for acetylene and hydrogen chloride molecule, therefore active raising is fairly obvious; The specific area of catalyst is the key factor that affects catalytic activity in addition, and lower content of metal can also keep the huge specific area of active carbon to greatest extent, and the appearance carbon ability of catalyst is strengthened, thus the life-span of extending catalyst.Therefore in the time that ordinary skill chloride auxiliary agent exceedes 1%, the specific surface of catalyst reduces, the life-span of catalyst be obviously affected (seeing contrast reaction embodiment 5).
The preparation method of catalyst of the present invention can be undertaken by following preferred embodiment:
First absorbent charcoal carrier is dried to 24 hours in 120 ℃ of baking ovens, then gets a certain amount of absorbent charcoal carrier for subsequent use; Take the soluble-salt of a certain amount of one or more noble metals and the soluble-salt of a certain amount of one or more common metals according to carried by active carbon weight, be dissolved in a certain amount of methyl alcohol or ethanol and obtain catalyst impregnating solution, the quality of methyl alcohol or ethanol is 2 times of carried by active carbon weight; Above-mentioned absorbent charcoal carrier is placed in to catalyst impregnating solution and floods 24 hours, then under 120 ℃ of conditions, dry 24 hours, obtain finished catalyst.
Further describe by the following examples technical scheme of the present invention and effect, it should be appreciated by those skilled in the art that following embodiment, only for the present invention is described, does not really want to limit the scope of the invention.
Embodiment
Catalyst Preparation Example 1
Absorbent charcoal carrier is dried to 24 hours in 120 ℃ of baking ovens, and the absorbent charcoal carrier of then getting 97.8 grams is for subsequent use; Measure 4 milliliters of the gold chloride ethanolic solutions of gold content 0.01 grams per milliliter, measure 10 milliliters of the copper chloride ethanolic solutions of copper content 0.1 grams per milliliter, be dissolved in 200 milliliters of ethanol and obtain catalyst impregnating solution; Above-mentioned absorbent charcoal carrier is placed in to catalyst impregnating solution and floods 24 hours, then under 120 ℃ of conditions, dry 24 hours, obtain containing 0.04% gold medal, the finished product catalyst without mercury of 1% bronze medal, by reaction, embodiment 1 evaluates.
Catalyst Preparation Example 2
Absorbent charcoal carrier is dried to 24 hours in 120 ℃ of baking ovens, and the absorbent charcoal carrier of then getting 97.4 grams is for subsequent use; Measure 2 milliliters of the gold chloride methanol solutions of gold content 0.01 grams per milliliter, measure 8 milliliters of the copper chloride methanol solutions of copper content 0.1 grams per milliliter, be dissolved in and in 200 ml methanol, obtain catalyst impregnating solution; Above-mentioned absorbent charcoal carrier is placed in to catalyst impregnating solution and floods 24 hours, then under 120 ℃ of conditions, dry 24 hours, obtain containing 0.02% gold medal, the finished product catalyst without mercury of 0.8% bronze medal, by reaction, embodiment 2 evaluates.
Comparative catalyst's Preparation Example 1
Absorbent charcoal carrier is dried to 24 hours in 120 ℃ of baking ovens, and the absorbent charcoal carrier of then getting 99.8 grams is for subsequent use; 4 milliliters of gold chloride ethanolic solutions that measure gold content 0.01 grams per milliliter, are dissolved in 200 milliliters of ethanol and obtain catalyst impregnating solution; Above-mentioned absorbent charcoal carrier is placed in to catalyst impregnating solution and floods 24 hours, then under 120 ℃ of conditions, dry 24 hours, obtain the finished product catalyst without mercury that contains 0.04% gold medal, react embodiment 1 by contrast and evaluate.
Comparative catalyst's Preparation Example 2
Absorbent charcoal carrier is dried to 24 hours in 120 ℃ of baking ovens, and the absorbent charcoal carrier of then getting 98.1 grams is for subsequent use; 10 milliliters of copper chloride ethanolic solutions that measure copper content 0.1 grams per milliliter, are dissolved in 200 milliliters of ethanol and obtain catalyst impregnating solution; Above-mentioned absorbent charcoal carrier is placed in to catalyst impregnating solution and floods 24 hours, then under 120 ℃ of conditions, dry 24 hours, obtain the finished product catalyst without mercury that contains 1% bronze medal, react embodiment 2 by contrast and evaluate.
Reaction embodiment 1
Get 10ml low noble metal catalyst without mercury finished product, in catalyst, contain 0.04% gold, 1% copper, pack catalyst into tubular fixed-bed reactor, then reaction bed temperature is controlled to 150 ℃, pass into reactor feed gas, reaction raw materials gas ratio is: hydrogen chloride/acetylene (volume ratio)=1.1, volume ratio (the volume space velocity)=20h of reaction raw materials gas flow rate and catalyst
-1, reaction afterproduct by gc analysis result is: conversion of alkyne 95.5%, vinyl chloride selective 98%.React after 100 hours catalyst activity, selectively constant.
Contrast reaction embodiment 1
Get 10ml low noble metal catalyst without mercury finished product, in catalyst, contain 0.04% gold, pack catalyst into tubular fixed-bed reactor, then reaction bed temperature is controlled to 150 ℃, pass into reactor feed gas, reaction raw materials gas ratio is: hydrogen chloride/acetylene (volume ratio)=1.1, volume ratio (the volume space velocity)=20h of reaction raw materials gas flow rate and catalyst
-1, reaction afterproduct by gc analysis result is: conversion of alkyne 56.5%, vinyl chloride selective 98%.React after 6 hours, catalyst activity reduction is: conversion of alkyne 46.2%, vinyl chloride selective 98.5%.
Contrast reaction embodiment 2
Get 10ml low noble metal catalyst without mercury finished product, in catalyst, contain 1% copper, pack catalyst into tubular fixed-bed reactor, then reaction bed temperature is controlled to 150 ℃, pass into reactor feed gas, reaction raw materials gas ratio is: hydrogen chloride/acetylene (volume ratio)=1.1, volume ratio (the volume space velocity)=20h of reaction raw materials gas flow rate and catalyst
-1, reaction afterproduct by gc analysis result is: conversion of alkyne 26.5%, vinyl chloride selective 98%.React after 6 hours, catalyst activity reduction is: conversion of alkyne 18.2%, vinyl chloride selective 98.6%.
Contrast reaction embodiment 3
Get 10ml low noble metal catalyst without mercury finished product, in catalyst, contain 0.3% gold, pack catalyst into tubular fixed-bed reactor, then reaction bed temperature is controlled to 150 ℃, pass into reactor feed gas, reaction raw materials gas ratio is: hydrogen chloride/acetylene (volume ratio)=1.1, volume ratio (the volume space velocity)=20h of reaction raw materials gas flow rate and catalyst
-1, reaction afterproduct by gc analysis result is: conversion of alkyne 98.5%, vinyl chloride selective 98%.React after 100 hours catalyst activity, selectively constant.
Contrast reaction embodiment 4
Get 10ml low noble metal catalyst without mercury finished product, in catalyst, contain 0.3% gold, 1% copper, pack catalyst into tubular fixed-bed reactor, then reaction bed temperature is controlled to 150 ℃, pass into reactor feed gas, reaction raw materials gas ratio is: hydrogen chloride/acetylene (volume ratio)=1.1, volume ratio (the volume space velocity)=20h of reaction raw materials gas flow rate and catalyst
-1, reaction afterproduct by gc analysis result is: conversion of alkyne 98.9%, vinyl chloride selective 98%.React after 100 hours catalyst activity, selectively constant.
Contrast reaction embodiment 5
Get 10ml low noble metal catalyst without mercury finished product, in catalyst, contain 0.04% gold, 3% copper, pack catalyst into tubular fixed-bed reactor, then reaction bed temperature is controlled to 150 ℃, pass into reactor feed gas, reaction raw materials gas ratio is: hydrogen chloride/acetylene (volume ratio)=1.1, volume ratio (the volume space velocity)=20h of reaction raw materials gas flow rate and catalyst
-1, reaction afterproduct by gc analysis result is: conversion of alkyne 95.5%, vinyl chloride selective 98%.React after 100 hours conversion of alkyne 85.5%, vinyl chloride selective 97.8%.
Reaction embodiment 2
Get 10ml low noble metal catalyst without mercury finished product, in catalyst, contain 0.02% gold, 0.8% copper, pack catalyst into tubular fixed-bed reactor, then reaction bed temperature is controlled to 150 ℃, pass into reactor feed gas, reaction raw materials gas ratio is: hydrogen chloride/acetylene (volume ratio)=1.1, volume ratio (the volume space velocity)=20h of reaction raw materials gas flow rate and catalyst
-1, reaction afterproduct by gc analysis result is: conversion of alkyne 91.6%, vinyl chloride selective 98%.React after 100 hours catalyst activity, selectively constant.
Reaction embodiment 3
Get 10ml low noble metal catalyst without mercury finished product, in catalyst, contain 0.04% gold, 0.4% copper, pack catalyst into tubular fixed-bed reactor, then reaction bed temperature is controlled to 150 ℃, pass into reactor feed gas, reaction raw materials gas ratio is: hydrogen chloride/acetylene (volume ratio)=1.1, volume ratio (the volume space velocity)=20h of reaction raw materials gas flow rate and catalyst
-1, reaction afterproduct by gc analysis result is: conversion of alkyne 93.7%, vinyl chloride selective 98%.React after 100 hours catalyst activity, selectively constant.
Reaction embodiment 4
Get 10ml low noble metal catalyst without mercury finished product, in catalyst, contain 0.01% gold, 1% copper, pack catalyst into tubular fixed-bed reactor, then reaction bed temperature is controlled to 200 ℃, pass into reactor feed gas, reaction raw materials gas ratio is: hydrogen chloride/acetylene (volume ratio)=1.1, volume ratio (the volume space velocity)=120h of reaction raw materials gas flow rate and catalyst
-1, reaction afterproduct by gc analysis result is: conversion of alkyne 55.6%, vinyl chloride selective 98%.React after 100 hours catalyst activity, selectively constant.
Reaction embodiment 5
Get 10ml low noble metal catalyst without mercury finished product, in catalyst, contain 0.04% platinum, 0.8% zinc, pack catalyst into tubular fixed-bed reactor, then reaction bed temperature is controlled to 150 ℃, pass into reactor feed gas, reaction raw materials gas ratio is: hydrogen chloride/acetylene (volume ratio)=1.1, volume ratio (the volume space velocity)=20h of reaction raw materials gas flow rate and catalyst
-1, reaction afterproduct by gc analysis result is: conversion of alkyne 89.8%, vinyl chloride selective 98%.React after 100 hours catalyst activity, selectively constant.
Reaction embodiment 6
Get 10ml low noble metal catalyst without mercury finished product, in catalyst, contain 0.04% ruthenium, 0.8% iron, pack catalyst into tubular fixed-bed reactor, then reaction bed temperature is controlled to 150 ℃, pass into reactor feed gas, reaction raw materials gas ratio is: hydrogen chloride/acetylene (volume ratio)=1.1, volume ratio (the volume space velocity)=20h of reaction raw materials gas flow rate and catalyst
-1, reaction afterproduct by gc analysis result is: conversion of alkyne 90.2%, vinyl chloride selective 98%.React after 100 hours catalyst activity, selectively constant.
Reaction embodiment 7
Get 10ml low noble metal catalyst without mercury finished product, in catalyst, contain 0.04% iridium, 1% copper, pack catalyst into tubular fixed-bed reactor, then reaction bed temperature is controlled to 150 ℃, pass into reactor feed gas, reaction raw materials gas ratio is: hydrogen chloride/acetylene (volume ratio)=1.1, volume ratio (the volume space velocity)=20h of reaction raw materials gas flow rate and catalyst
-1, reaction afterproduct by gc analysis result is: conversion of alkyne 78.2%, vinyl chloride selective 98%.React after 100 hours catalyst activity, selectively constant.
Reaction embodiment 8
Get 10ml low noble metal catalyst without mercury finished product, in catalyst, contain 0.04% palladium, 0.8% copper, pack catalyst into tubular fixed-bed reactor, then reaction bed temperature is controlled to 150 ℃, pass into reactor feed gas, reaction raw materials gas ratio is: hydrogen chloride/acetylene (volume ratio)=0.9, volume ratio (the volume space velocity)=20h of reaction raw materials gas flow rate and catalyst
-1, reaction afterproduct by gc analysis result is: conversion of alkyne 60.2%, vinyl chloride selective 98%.React after 100 hours catalyst activity, selectively constant.
Reaction embodiment 9
Get 10ml low noble metal catalyst without mercury finished product, in catalyst, contain 0.04% gold, 0.8% copper, pack catalyst into tubular fixed-bed reactor, then reaction bed temperature is controlled to 200 ℃, pass into reactor feed gas, reaction raw materials gas ratio is: hydrogen chloride/acetylene (volume ratio)=1.2, volume ratio (the volume space velocity)=120h of reaction raw materials gas flow rate and catalyst
-1, reaction afterproduct by gc analysis result is: conversion of alkyne 31.2%, vinyl chloride selective 98%.React after 100 hours catalyst activity, selectively constant.
Reaction embodiment 10
Get 10ml low noble metal catalyst without mercury finished product, in catalyst, contain 0.01% platinum, 0.01% gold, 0.5% copper, 0.5% zinc, packs catalyst into tubular fixed-bed reactor, then reaction bed temperature is controlled to 150 ℃, pass into reactor feed gas, reaction raw materials gas ratio is: hydrogen chloride/acetylene (volume ratio)=0.9, volume ratio (the volume space velocity)=20h of reaction raw materials gas flow rate and catalyst
-1, reaction afterproduct by gc analysis result is: conversion of alkyne 91.2%, vinyl chloride selective 98%.React after 100 hours catalyst activity, selectively constant.
Claims (9)
1. for a low noble metal catalyst without mercury for acetylene hydrochlorination reaction, described catalyst comprises absorbent charcoal carrier; The mixed active component that one or more precious metal chemical complexs and one or more common metal compounds form according to a certain percentage, the 0.01-0.04% that wherein mass content of noble metal is described quality of activated carbon, the mass content of common metal is the 0.1-1% of described catalyst gross mass, described noble metal is selected from gold, palladium, ruthenium, platinum and iridium, described common metal chosen from Fe, zinc and copper.
2. catalyst according to claim 1, the 0.02-0.04% that the mass content that it is characterized in that described noble metal is described quality of activated carbon, the 0.5-0.8% that the mass content of described common metal is described quality of activated carbon.
3. catalyst according to claim 1 and 2, is characterized in that described precious metal chemical complex is the soluble-salt of described noble metal, preferably chloride, sulfate, phosphate or nitrate, more preferably chloride.
4. according to the catalyst described in any one in claim 1-3, it is characterized in that the soluble-salt that described common metal compound is described common metal, preferably chloride, sulfate, phosphate, nitrate etc., more preferably chloride.
5. according to the catalyst described in any one in claim 1-4, it is characterized in that the vinyl chloride that described catalyst is realized in acetylene hydrochlorination reaction is selectively not less than 97%, preferably more than 98%.
6. according to the catalyst described in any one in claim 1-5, it is characterized in that catalytic activity and the catalytic selectivity of described catalyst in the time that acetylene hydrochlorination reaction is carried out 100 hours is constant.
7. the preparation method of the low noble metal catalyst without mercury for acetylene hydrochlorination reaction according to claim 1 and 2, the method is carried out as follows: absorbent charcoal carrier is dry; Then take the soluble-salt of a certain amount of one or more noble metals and the soluble-salt of a certain amount of one or more common metals according to carried by active carbon weight, be dissolved in and in methyl alcohol or ethanol, obtain catalyst impregnating solution; Above-mentioned absorbent charcoal carrier is placed in to catalyst impregnating solution dipping, dries, obtain finished catalyst.
8. preparation method according to claim 7, described soluble-salt is chloride, sulfate, phosphate or nitrate, preferably chloride.
9. one kind is utilized the method for the low noble metal catalyst without mercury catalyzing acetylene preparing vinyl chloride by hydrochlorination described in any one in claim 1-6, the method is carried out as follows: a certain amount of described catalyst is placed in to tubular fixed-bed reactor, reaction temperature 120-220 ℃, pass into reaction raw materials gas hydrogen chloride and acetylene, reaction raw materials gas ratio is: the volume ratio=0.9-1.2 of hydrogen chloride/acetylene, the volume ratio=10-120h of reaction raw materials gas flow rate and catalyst
-1.
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